Stabilization of vinylidene chloride resins



Patented July 29, 1952 Jacob n. Matlack, Picatinny Arsenal; N. r, andRobert J. Reid, Canal Fulton, Ohio, assignors to The Firestone Tire &Rubber Company, Akron, Ohio, a. corporationof Ohio No Drawing.Application June16, 1951,

Serial No. 232,048v

4 Claims. (Cl. 26023) t This invention relates to the stabilization,against the action of heat in extrusion and other fabrication, ofcrystalline vinylidene chloride resins. v

Crystalline, fiber-forming vinylidene chloride polymers and copolymersare rather sensitive to heat, and cannot be melt-extruded'without theaddition of heat-stabilizing agents. The requiremerits for such aheat-stabilizing agent are ricinoleate obtained in accordance with thebroader aspects of this invention, have particularly desirable extrusionand other working properties.

THE VINYLIDENE CHLORIDE POLYMERS' AND COPOLYMERS The resins forming thebasis of the composl rather eXa-cting- First, e agent must be tions ofthis invention are a well-known class pable of stabilizing the resins atthe high temof polymers of vinylidene chloride and copolymers peratureand for the extended periods involved thereof it not more than of otherun- 'li extr i p o and must o itself be saturated compoundscopolymerizable therewith, affected y these conditions. Secondly, the hat and correspondingly containing at least 85% of stabilizer must becompatible with the resin, both 15 vinylidene chloride copulymerizedtherein, such in the fused and in the solidified states. Finally, resinsare characterized by crystalline behavior, the heat stabilizer must notbe antagonistic i. e. theyiuse sharply to form relatively fluid .towardthe plasticisers, light stabilizers and other lt hich may be extruded,quenched and compounding ingredients which u be co oriented to formstrong filaments of crystalline rated into e resins character. Asyndrome of this crystalline habit Accordingly, it is an object of thisinvention i the recalcitrance of these resins to compoundto providenovel and satisfactory 'vinylidene m t ma romolecules of polyvinylidenehl rid r s n p s ti schloride prefer contact with each other and tendAnother object is to provide a ove heal? to reject any foreignsubstances such as plastiil r r vinylidene chloride resins cisers,stabilizers and the like. It is therefore very A further Object is toProvide a novel comblnadifficult to provide suitable compounding agentslion, w Said Stabilizer, f Ot Compounding for these resins, and inparticular to provide mgred1nt$ having particularly advantageousmutually compatible combinations of'plasticisar properties. tion, heatstabilization and age resistance; The SYNOPSIS OF THE INVENTION 3Obarium recinoleate involved in the applicants The above and other 010.6t d composition is readily compatible with these c S are sequre m resinsand does not interfere with any of the accordance with this invention,by the incorpoknown other compounding ingredients used with ration, into100 parts by weight of a vinylidene vinyhdene chloride g gggfi ig &g gggg fg '0 partfls banum As noted above, the base resin may be ahomo-vcompositions. have polymer of vinyliden chloride, or a copolymeroutstanding resistance to degradation by heat thereof with other u atated m as and mechanical working, and tolerate any of the which 0 1 t m00 pom other compounding agents-p1asticisers, lubri- 0P0 ymeljs mus atleast-185% cants, heat stabilizers etc.known as being suit- 40 Vmyhdenechloltlde copolymenzed therem P V. on the total weight of the copolymer.Suitable able for use in vinylidene chloride resins. The f r stabilizerof this invention yields particularly cqmonomers. or i purpose for examp1e favorable results in combination with diphenyl vmyl vmyl Vmyl acetateether and glycidyl. phenyl ether, the resultant styrene, acrylic andmethacrylic esters such as preferred compositions lying within thefollowing methyl Flthacrylate, ethy} a y fi and the limits, all partsbeing given by Weight: acrylomtrile, methacrylonitrile, vinyl ethers andI ketones such as methyl vinyl ether, methyl vinyl TABLE I ketone andrelated compounds such as methyl I Parts isopropenylketones and thelike. For'a' more V nyhdene chloride polymer orv copoly1ner 100 completelist of compounds known to copory; DlphPnyl-ether 54(3) merize withvinylideneemoride see Krbzn 122 13151 2:2 t Kurzes Handbuch derPolymerisationstechnik V H V 1 Mehrstofipolymerization Edwards Bros;These specific preferred compositions, lbesides I the items indent d u rv y having'the excellent heat resistance of the barium T SUBSIDIARYCOMPOUNDING INGREDIENTS As noted above, the present invention isdirected principally to the stabilization of the vinylidene chlorideresins against heat, and not to the imparting of any other benefit tothe resin. In order to plasticise the resins, or to render the same moreresistant to light (as in filaments extruded therefrom and destined forapplications involving exposure to weathering) specific additionalingredients must be incorporated into the resin. The barium recinoleateof this invention is particularly advantageous in that it is notantagonistic to any of these other ingredients commonly employed, i. e.,it will not interfere with the function of these other agents, nor willit cause them to efiloresce on the surface of the articles ultimatelymade from the compositions. A number of materials are used as lightstabilizers, plasticisers and other compounding agents in. vinylidenechloride resins and may be used in conjunction with the bariumricinoleate of this invention, typical materials of this sort beingchlorinated benzenes, naphthalenes and diphenyls; aryl and aralkylethers, particularly those containing an epoxypropyl group;dihydroxy-benzophenones; phenolic compounds; and aryl and alkylated arylsalicylates. In addition, several other ingredients, not claimed in thepresent application, such as liquid low molecular weightpoly-alpha-methyl styrenes having viscositiesat 60 C. ranging from 50 to1000 centipoisescondensates or bisphenol A with epichlorohydrin(believed to have the structure,

of these compounds. In each case, the several ingredients were slurriedtogether with petroleum ether, and the slurry dried. The dried slurrywas then ball-milled for 20 minutes, and compression molded at 335 F. toform a solid-preform button which was then extruded in a piston-typelaboratory extruder into a water-quenching bath and thereafter orientedby passage successively over snubbing and stretching rolls. Conditionsof extrusion and'orientation were as follows:

TABLE II Temperature of piston chamber heating medium 365 F. Pistondisplacement 0.652 ml. per

minute Die construction u nickel, with .020 inch diameter 7 orificeTemperature of die 320 F. Rate of withdrawal of filament from die beforequench 15 feet per minute Temperature of quenching bath 15; C.

Filament orientation 400% Diameter of filament 8 mils Samples of theoriented filament were removed during each run at intervals of 5,, 15and 3!! aromatic hydrocarbon condensates from petroleun fractions, etc.Barium ricinoleate is likewisepompatible, and non-interferin with theselatter compounding ingredients.

' also noted above, the invention in one of its;specifi c. aspectsrelates to a particularly favorable fcombination of the bariumricinoleate with diphenyl ether and glycidyl phenyl ether withintheicompositional limits set out in Table I above. These specificcompositions are characterized by particularly smooth extrusion andorientation behavior; ability to withstand normal extrusion temperatures(320-340'F.) for extended periods of time; and ability to withstand evenhigher temperatures, such as result from temporary excursionsof thecontrol equipment, for periods of time'sufiicient for restoration of theproper extruding conditions.

With the foregoing-general discussion in mind, there are given herewithdetailed examples of thepractice of this invention. All parts givenareby weight.

Example I Parts vinylidene chloride. resin .(copolymer of 85%vinylidene. chloride, 15% vinyl chloride) v100 Diphenyl ether 8 Bariumricinoleate V .1 .pr 2 fil cidylp nyl ether 1 12 Two compositions weremade up in accordance with theforegoing-one containing one part-each of..thebarium ricinoleate and glycidyl phenylether, and the othercontaining two partseach minutes from the beginning of operation, andsubjectively rated by the operator as to appear ance. Each run wascontinued untilthe resin-,in the extruder began to decompose, whichtime-was recorded as the decomposition time. .Set forth in Table. IIIare the observations made.

TABLE III Parts of Barium Ricinoleate. and oi Glycidyl: 1

Phenyl Ether Used .2

Decomposition time (minutes) Appearance of filament during extrusion, at

vinylidene chloride resin (copolymer of vinylidene chloride, 15 .vinylchloride) ;l00 Alpha-methyl styrene polymer (low molec ular' weight,viscosity c entipoises Vinylidene chloride resin (copolymer of 85%vinylidene chloride, 15% vinyl chloride) Panafiex BN-l (an aromatichydrocarbon condensate manufactured by Pan American Chemicals Corp.) 3Condensate, under etherification conditions, of bisphenol A withepichlorohydrin (largely a diether of the formula (0cmoH-oH2-0)o orn)2 2Barium ricinoleate 2 Two compositions were made up, one in accordancewith each of the recipes A and B above. Each composition was extrudedand oriented by the process described in Example I. The follow ingobservations were made.

TABLE IV Recipe Used A B Decomposition time (minutes) 37 26 Appearanceof filament during extrusion at excellent.

iib'dr said vinylidene chloride resin being selected from the groupconsisting of polymers of vinylidene chloride and copolymers thereofwith other'un- 6 saturated compounds copolymerizable therewithcontaining at least of vinylidene chloride copolymerized therein.

2. A heat-stable, smoothly melt-extrudable composition comprising, byweight:

Parts A crystalline vinylidene chloride resin Diphenyl ether 8 Glycidylphenyl ether 2 Barium ricinoleate 2 said vinylidene chloride resin beinga copolymer of 85% by weight of vinylidene chloride with 15% by weightof vinyl chloride.

3. Anoriented-crystalline resinous filament comprising by weight:

- Parts A crystalline vinylidene chloride resin 100 Diphenyl ether 5-10Glycidyl phenyl ether 1-3 Barium ricinoleate 1-3 said vinylidenechloride resin being a copolymer of 85% by weight of vinylidene chloridewith 15% by weight of vinyl chloride.

4. An oriented-crystalline resinous filament comprising by Weight:

Parts A crystalline vinylidene chloride resin 100 Diphenyl ether 8Glycidyl phenyl ether 2 Barium ricinoleate 2 said vinylidene chlorideresin being a copolymer of 85% by weight of vinylidene chloride with 15%by weight of vinyl chloride.

JACGB D. MA'ILACK. ROBERT J. REID.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,233,442 Wiley Mar. 4, 19412,564,646 Leistner et al Aug. 14-, 1951 OTHER REFERENCES ModernPlastics, Dec. 1949, pages 111-112.

1. A HEAT-STABLE, SMOOTHLY MELT-EXTRUDABLE COMPOSITION COMPRISING BYWEIGHT: